Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β-bromo-α-cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine- or phosphine-catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported.     

Melt spinning of propylene carbonate‐plasticized poly(acrylonitrile)‐co‐poly(methyl acrylate)

The primary use of poly(acrylonitrile) (PAN) fibers, commonly referred to as acrylic fibers, is in textile applications like clothing, furniture, carpets, and awnings. All commercially available PAN fibers are processed by solution spinning; however, alternative, more cost‐effective processes like melt spinning are still highly desired. Here, the melt spinning of PAN‐co‐poly(methyl acrylate) (PMA) plasticized with propylene carbonate (PC) at 175°C is reported. The use of methyl acrylate (MA) as comonomer and PC as an external plasticizer renders the approach a combination of internal and external plasticization. Various mixtures of PAN and PC used in this work were examined by rheology, subjected to melt spinning, followed by discontinuous and continuous washing, respectively. The best fibers were derived from a PAN‐co‐PMA copolymer containing 8.1 mol‐% of MA having a number‐average molecular weight M _n of 34 000 g/mol, spun in the presence of 22.5 wt.‐% of PC. The resulting fibers were analyzed by scanning electron microscopy and wide‐angle X‐ray scattering (WAXS), and were subjected to mechanical testing.     

Identification of the Isomeric Dideutero p-Benzoquinones by 13C-H and 13C-D Coupling Constants

2,5- and 2,6-dideuterobenzoquinone-1,4 were prepared by a direct catalytic (NaBD₄/PdCl₂) exchange of bromine in the corresponding dibromo derivatives and the subsequent oxidation with Ag₂O. The structure of the products was unambiguously established by proton-carbon and deuteron-carbon splitting pattern of their NMR spectra.     

Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors

This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)₂SiC₆H₄PPh₂ ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC₆H₄PPh₂) with chlorosilylene (PhC(NtBu)₂SiCl). Treatment of 1 with Se and GeCl₂ resulted in Si^IV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl₂ leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl₂ and AlCl₃ resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl₂ and GaCl₃ forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu⁺ and [CuCl₂]⁻. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.     

Ultrastructure of the Alabama argillacea (Hübner) (Lepidoptera: Noctuidae) midgut

The insect midgut has ultimately been the focus of researches tempting to control insect pests because alterations in the insect gut may affect not only its development, but also physiological events such as nutrient absorption and transformation. The objective of the present work was to describe morphologically, histochemically, and ultrastructurally the larva midgut of Alabama argillacea (Hübner) (Lepidoptera: Noctuidae), a cotton key pest in Brazil. Light and electronic transmission microscopy was used to obtain images from midgut sections of late fourth-instar larvae of A. argillacea. In general, the morphology, histochemistry, and ultrastructure characteristics of A. argillacea midgut follow that described in the literature for other lepidopteran species. However, the results showed a mitochondrial polymorphism and branched microvilli, which suggest an ultrastrucutural and physiological modification possibly associated with a high absorption and secretion activity by the columnar cells of this species. This intense activity may favor a faster response related to the action of ingested microbial agents and/or toxins, and can explain the high susceptibility of A. argillacea to the agents of control such as the toxin of Bacillus thuringiensis.     

Kinetic Studies of the Thermal cis-to-trans Isomerization of Dioxaphospholanes

By following a previously reported method,¹ the synthesis of r-2-alkoxy-cis-4-cis-5-dimethyl-1,3,2-λ³-dioxaphospholanes ligands (1 and 3) was carried out. The purpose of this work is the kinetic study of the inversion barrier at phosphorus for 1 and 3 and the comparison with the already informed dioxaphospholane 2. The kinetic measurements of the thermal isomerization cis-to-trans were performed by ³¹P NMR spectroscopy, observing a first order kinetics for both compounds. The energy of activation (E_a) for the epimerization of compounds cis-1 and cis-3 was calculated to be 16.0 ± 0.6 and 11.8 ± 0.8 kcal/mol, respectively. The values of the thermodynamic parameters of the transition state (Δ H^≠, Δ S^≠, Δ G^≠) suggest that the inversion at phosphorus not only depends on the spatial requirements of the alkoxy substituent but also on entropic effects. The thermodynamic parameters Δ H°, Δ S°, and Δ G° were also evaluated and they show that the cis isomers are preferred from enthalpic point of view, but entropic effects dominate the equilibrium trans ? cis leading to the entropically favored trans isomers. Furthermore, the results are supported by density functional theory calculations of 1–4 at the B3LYP/6-31G** level.     

Testing an alternative search algorithm for compound identification with the ‘Wiley Registry of Tandem Mass Spectral Data,MSforID’

A tandem mass spectral database system consists of a library of reference spectra and a search program. State‐of‐the‐art search programs show a high tolerance for variability in compound‐specific fragmentation patterns produced by collision‐induced decomposition and enable sensitive and specific ‘identity search’. In this communication, performance characteristics of two search algorithms combined with the ‘Wiley Registry of Tandem Mass Spectral Data, MSforID’ (Wiley Registry MSMS, John Wiley and Sons, Hoboken, NJ, USA) were evaluated. The search algorithms tested were the MSMS search algorithm implemented in the NIST MS Search program 2.0g (NIST, Gaithersburg, MD, USA) and the MSforID algorithm (John Wiley and Sons, Hoboken, NJ, USA). Sample spectra were acquired on different instruments and, thus, covered a broad range of possible experimental conditions or were generated in silico. For each algorithm, more than 30 000 matches were performed. Statistical evaluation of the library search results revealed that principally both search algorithms can be combined with the Wiley Registry MSMS to create a reliable identification tool. It appears, however, that a higher degree of spectral similarity is necessary to obtain a correct match with the NIST MS Search program. This characteristic of the NIST MS Search program has a positive effect on specificity as it helps to avoid false positive matches (type I errors), but reduces sensitivity. Thus, particularly with sample spectra acquired on instruments differing in their setup from tandem‐in‐space type fragmentation, a comparably higher number of false negative matches (type II errors) were observed by searching the Wiley Registry MSMS. Copyright © 2013 John Wiley & Sons, Ltd.